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C. P. NEZERAUX.

SECONDARY BATTERY.

Patentedfeb. 6,1883.

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. Ytorride are bad conductors) ci 'UNTTsD STATns PATENT Trice,

CHARLES PLAOIDE NZERAUX, OF PARIS, FRANCE.

SECONDARY-BATTERY.

SPECIFICATIGN forming part of Letters Patent'No. 271,732, dated February6, 1883.

Application filed September 26, 1882. (No modeLl Patented in France June23, 188:2, in Belgium September il. 1.882, and in England June 2s, lese,No. 3,030.

To all 'whom it may concern Be it known that I, CHARLES PLACIDE N13`-ZERAUX, a citizen of the Republic of France, residing at Paris, France,have invented an Improved Secondary Battery, (For which I have obtainedLetters Patent in France, June 23,1882; Belgium, September2,1882;England, June28, 1882, No. 3,030;) and Ido hereby declare that thefollowing is a full, clear, and exact description ot' the invention,which will enable othersv skilled in the art to which it appertains tomake and use the same, reference being had to the accompanying;drawings, and to the letters or figures ot' reference marked thereon,which form a part ot' this specification.

According to Monsieur Gaston Plante, the learned French chemist, whentwo plates ot' lead, plunged into abath acidulated with about one-tenthof sulphnric acid, are submitted to the action of a galvanic current ofsuieie'nt strength, oxygen appears almost immediately on one of theplates, which becomes covered with a thin layer ot' peroxide, while, onthe other band, hydrogen quickly appears on the other plate after havingreduced the thin layer of oxide with which the same has been covered byits exposure to the air, and it' at the end ot' a l'ew instants thesecondary current produced by the apparatus is tried it is found thatthis current is already very strong, but of short duration. If theprimary current is again passed a certain number ot' times, the polesbeing reversed, the layers of oxide alternately formed or reduced becomethicker and the secondary effects which result are ol' longer durationand greater intensity. In any case, however, only a very limitedthickness can be given to the said layers, so that in order to store upany considerable quantity of electromotive force it is necessary to givea very large extent of surface to the'polar plates, which renders theapparatuses heavy and cumbersome. ln order to reduce or obviate thisinconvenience, Monsieur Faure deposits upon the polar plates of ananalogous'couple a thicker layer of oxide, which he afterward submits tothe primary current. In this way he accumulates a largerqnantity offorce; but the resistance of the current increasing` with the thicknessof the layers ot' oxitle loss ot' uset'ul effect, making it necessary tokeep the thickness of these layers tolerably small. The Faure battery,therefore, like that of Plante, is heavy and oun'ibersome.

The two above-nain ed batteries have, besides these, the followinginconveniences, which are still lnore serious: first., they only receivethe charge slowly by reason ofthe feeble relative development of thepolar plates, which, as is the case with condensation-surl'aces,-cannotreceive more than suits their extent; second, the number ol' pilescomposing a battery cannot be increased or decreased easily and atpleasure without destroying the galvanic current; third, the putting towork is difticult to manipulate, because each pile carries screwterininals, which serve to connect them togetherby means of conductors,and as the parts in contact easily oxidize it is necessary to clean orrevive them often with care, which necessitates long and minute work,for a single badlyconducting contact is suiticient to reduce or even toprevent completely the action ot' the current; fourth, a fresh supply ofelectro-motive force cannot be accumulated af'ter discharge withouthaving recourse, as in the iirst instance, to a snfcient source ofelectricity acting upon the apparatuses themselves, which renders it.absolutely necessary, it' the requisite material is not at hand, totransport the batteries to the place where there is a special andsuitable apparatus for effecting the charge, unless, indeed, thecharging is effected in place by means of conductors-aftrrangementswhich give rise to serious complications and produce inferior results.

It is chiefly to remedy the inconveniences above pointed out that I haveinvented the system ot which the following is a description:

Figures l and2of the annexed drawings represent a couple, in which A andB are two plates the ebonite, being merely framed therein, suchframesprojecting beyond the working-surfaces, as shown.

The perfect adhesion ot' the caoutchouc to the lead plates is easilyobtained by ba king the plastic material on the metal at a suitable heatwin32 purpose. Theplatesofleadthusinclosedeverywherein a rigid adherentframe require a solid- Aity they would not otherwisehave, and areperfectly insulated at all the parts thus covered. Each element of thccouplecarries at its head the projections s s', which rest on thesmallmetallic strips b 1),xed to the vessel It, which is lined with,frutta-porcina or lead V and contains the exciting-liquid. These smallconductingstrips serve as collectors of the electricity, and areprovided for this purpose with conducting terminals Y. The, polar plateof each element carries a lugo, inclosed in the thickness ot' the fra mewhich contains it, except at the line i t, where it comes in contactwith the strip b. 'Ihis lng is thickened up with a small plat.c,k, ofmetal soldered thereto. This plate k ispre'- erablv made of metal whichis not easily oxidized, and which is more resisting than the lead, inorder to avoid the too rapid wear ot the contact part 'i t. The twoelements of the couple being exactly similar and placed parallel to eachother in the vessel It, the cavities formed by the frames beine`opposite one another, it will be understood that by the contact ot' thelugs o they will be in communication,"'the one with the collector 7) andtheother with the collector b. It results from this arrangement thatwithout touching,r the terminals Y and without destroying the galvaniccurrent one may with the greatest case put in, take ont, or change atpleasure the couples of a battery in order to reduce or increase theelectro-motive force, and that by means of independent commutators thecouples may be connected in tension or in quantity.

In order to place the couples above described in a condition to furnisha certain electro-inotive torce, I proceed either in a direct orin anindirect manner, according to circumstances. 1 shall irst explain theindirect case, because it is the most interesting from an industrialpoint of view, and because the direct process will come out as aconsequence in the course of thedescription. Assuming, iirst of all,that a special manufactory, operating on a large scale and eronomically,supplies to industrial or other persons who employ my couples powders oflead peroxidized and reduced a certa-in number ot' times by a galvaniccurrentone part iinally reduced or metallized and the other part finallyperoXidized-I then operate as follows: I lill thepcavities U and l) inthe plates AB, one with reduced or metallized powders mixed with watercontaining an alkaline saltsuch as potassio cyanide, for example-and theother with the peroxidized powders mixed simply with water. I level thepulverulent layers to the frames with astraightedge, and I place theelements on an inclined plane to facilitate the draining away of theexcess of liquid. After an hour or more of draining the layers haveacquired aconsistence which allows of turning them over. I then put overeach layer ot' powder a woolen cloth, a piece ot' felt, or other spongyand unattackahlc material, d, and over al1 a rigid plate,c e,

perforated with a multitude of small holes, which plate I connect toeach element with india-rubber bands ff. A couple thus prepared andplungedinto abath acidulated with about one-tenth of sulphuric acid iscapable ot' furnishing during several days a supply ot' electricitypowerful in tension and in intensity. It' it is desired to reconstitutethis couple when exhausted more or less completely of chemical work, itis sufficient to remove the pulverulent layers from the lead plates withascraper or other means and to replace them by fresh powders keptcarefully in reserve, operating with them as l havejnst described. Theexhausted powders removed as above from the lead plates are taken to thespecial manufactory, where they are revivified and put into a conditionto serve again, and so on indefinitely. lt will be understood that thismanner ot' operating removes certain diiicnlties in practi-- calworking.

. In order to obtain the powders which are to serve in the formation ofmy couples, [employ chietiy the three following means:

The first consists in melting the required quantity of lead in anirouvessel, and in adding; thereto, alter fusion, one or two equivalentsof mercury/,so that the amalgam remains in a pasty condition aftercooling. After having carefully amalgamated the surface of the polarplates ot' the elements of one or more couples analogous to that alreadydescribed, l fill the cavities C and D with this amalgam, which I levelto the frames with the straightedge.v After the supcrabundant mercuryhas drained away, the metallic layers thus 0btained are very solid andadhere strongly to the polar plates, whereby any porous devices whateverfor holding such layers in place are dispensed with. rFliese couples,being plunged into an acidulated bath and submitted to the action ot' agalvanic current ol' sufficient strength, will act as follows: Thepositive layers will soon become covered with peroxide, beginning on thevisible surface, and afterward penetrating the mass in proportion to thegalvanic action and driving,r ont the inercnry, which falls to thebottom of the vessel. This goes on until the polar plaies are reached.At that moment the -mercury will have disappeared completely from theperoxidized lay! ers, which will then form a spongy net-work solidlyagglomerated. Itthe electric current is reversed, the amalgamated layersoftheother elementswill be peroxidized in tlieirturn,\vhile thosealready peroxidized will be reduced to the metallic state. By reversingthe direction ofthe current a number of times the peroxidized andreduced powders will acquire the maximum of their electro-motive force,which is very great if the discharge is etlected with IOO ITO

the same couples which have served for storing up the primary work. Inorder to utilize these agglomerated powders inthe couples, the action ofwhich is indirect, they are carefully removed from the frames andlightly ground separately in water to render them aristas a moreuniform, and they are afterward delivered for industrial consumption. Inorder to preserve the reduced powders from oxidation, it' they are notused immediately,-they areimniersed in water containing an alkalinesaltsuch as potassic cyanide, for example. The peroxidized powders maybe simply dried.

The second means consist in melting therequired quantity of lead andadding` thereto only a third ot' its weight of mercury. This amalgam,after cooling, is dry and t'riable, and is ground and sit'ted. Thepowder thus obtained is dry to the touch, very permeable, and a goodconductor of electricity. Placed in the cavities of the above-mentionedcouples, it peroXidizes well, driving oft' the mercury c ontained in it.and renders .an excellent useful effect, whether the discharge iseffected directlyorthe powders are used in other couples.

The third means consist in rasping pure lead, either by milling in wateror by means of a circular rasp having tolerably tine teeth acting onplates of from oneto two millimeters thickness, to facilitate the workland -to prevent the clicking oft-he teeth ot1 the rasp. rlhe powdersthus obtained` placed in my couples, also give good results, butinferior to those of the amalgamated powders.

In order to revivify the powders which have been used, the same processis employed as for the other powders. Theyare putinto special couplcsand are submitted to the primary current, whereby onepart is peroxidizedand the other part metallized, after which theyare removed and deliveredfor fresh use. It may be observed that if the work ot' revivitication iseiected in heated baths a more economical result is obtained.

From what precedes it will be seenthat the more economical the primarysource of power is the less will be the cost of' theelectro-motivet'orce furnished by my couples. Hydraulic machines andsteam-engines of great power,

working eXp-ansively and with condensation, driving dynamo-electricmachines, are, l believe, the best adapted for practically resolvinginmany cases, and in an economical manner, the important problem ot' powerand light by electricity.

Fig. 3 of the drawings represents a double element, the cavities E F ot'which are filled with powders held in place by the t'elts d d, theperforated plates c e, and the indiarubber bands ff. g g' are plates ofporous earthenware, placed between the velements of the couples toprevent polarization by hydrogen.

Fig. 4 represents also a double element, but without fcltsand perforatedplates. Its cavi. ties are furnished with lead powders amalgamated tosaturation.

Figs. 5 and G represent a couple for direct discharge, in which thevessel which usually contains the exciting liquid is suppressed. The twoelements in this case are connected to another frame, with which theymake a tight joint. rlhe -object otl this other frame is to leavebetween the porous layers a free space,

which is filled with tine sand or other substance. H I are small tubes,each closed with a screw-plug. They serve i'or filling the hollow spaceand for saturating the powders with acidulated water. Apparatuses thusarranged are easily handled and occupy little space.

Fig. 7 represents a battery formed ot' two series of piles, eachcomposed ofthe same number ot' couples, p q and p q', separated by thepartitions a a a a ot' the vessels A and B. The couples p q ot' theseries A are connected in tension by means ofthe conductors r r r, andthose ot' the series B are connected in quantity by means of theconductors s s s, the two series being in communication by the conductorT. If the circuit is closed with a dynamo-electric machine, {'orexample, by the conductors h h', a very energetic galvanic current willbe produced, which will set the machine in motion, and in proportion asthe couplesp q, connected in tension, accomplish their discharge, thecouples p q', connected in quantity,will receive in return and byaccumulation a certain remunerative work.' It by means of'lcommutators,an d after m ore orless complete disch arge of the couples p q, theselatter couples, p q, are connected in quantity and the couplcsp g intension, an inverse current will be produced in the battery, and thedynamoelectric machine will continue its motion. TheA result of thiscombination is that the smaller the loss of useful effect in eachdischarge the more frequently the galvanic current can be reversed.After exhaustion ot' these couples they may be reconstituted, either bymeans of a galvanic current acting directly on the couples themselves orby changing the powders. There may also be added to the piles in tensionany number of other piles capable of restoring as it is prod nced theloss ot' useful elt'ect ot' the electro-motive force. The maintenance inthis case will only amount to that ot' the additional piles.

1n order to charge my couples by means of a galvanic current, it 1s notindispensable to soak them in water containing sulphuric acid, as a goodresult can also be obtained with a solution'ot' sulphate ot' copper,potash, and certain other acid oralkaline baths.

The form ofthe apparatuses may be varied according to the purposes forwhich they are intended. The natureot' the materials employed in makingthe frames may also be varied, according tQ whether the baths in whichthe .couples are to work are acid, alkaline, heated,

or not heated.

The reduced and peroxidized powders employed in my couples l'or indirectdischarge can also be obtained by means ot' an oxide of lead submittedto the action ot' the primary current in the reviviiying apparatuses,but with TOC I-IO

less advantage than with the powders in the metallic state.

The small metallic strips serving as collectors may be replaced bymercury-cups, which complete the contact ot' the couples by means oflugs arranged to dip therein l'or that purpose.

The arrangements above described are applicable wherever electricity issusceptible of being usefully employed, espeeiullyfor the production ofpower or light, or for chemical de- 5 composicion, &o.

I claimi 1. The combination of thel vessel R aud its lining V and metalstrips b b with the plate A, havingr lug,r 0, projections s s', and withthe o plate K and terminal X,substantially as herein shown unddescribed.

2. rlhe hollow pluto A, having a filling of metallized lead powder andalkaline Salty, and tho porous covering d e, in combination with hollowplate B, having u filling of peroxidized 15 lend, und u porous covering,(l e, substantially us herein shown und described.

GH. P. NZERAUX.

iitnessesz A. BLTRY,

oBfr. M. Hooruu.

